Purification of hydrocarbon oils



Patented Jan. 6, 1931 CARBON r. DUIBBS, orwrnmnr'rn, ii mnors, comrnnx, or" onroaeo, rumors, A

COBBOBA'llION or sour]: DAKOTA PURIFICATION orHYnnocAa-Bon OILS Ili'oDrawing. Application filed June 29, 1925,

This invention relates to the purification of hydrocarbon oils, "and refers more par,- ticularly to the removal of objectionable sul phurous, odoriferous and: other deleterious compounds which rendertheproducts. oi the distillation of hydrocarbon oils under heat objectionable, either from theastandpoint of odor or instability V I 1.

In recent years oils have, been subjected to high temperatures, under high pressures in what is known as cracking, in order; to produce products havinga relatively lower boiling pointrange. The distillate and products obtained fromthe distillation of'these hydrocarbon oils under heat and pressure at the present time aregbeing subjected to several methods of refining, none of which seem to be entirelysatisfactory; For in stance, with oils having a high sulphur con tent, this sulphur content may be rcducedby subjecting the oil to the action of large quantities of strong sulphuric acid. This sulphuric acid is not only expensive, but its use results in an excessive loss of oil due to the oil being taken out by the acid. This excessive loss is probably due to the-iactthat knowledge is limited as to what sulphur compounds exist in the said distillate; I

I believe that when the charging oil is subjected to cracking temperatures, a high percentage: of the sulphur contained in that oil which comes overhead with the vaporizable fractions of said charging oil is in the form of sulphureted hydrogen produced by the combination of the sulphur withthe hydrogen of the oil. This sulphureted hydrogen can be very readily and economically removed from the distillate; I

However, there are other sulphur compounds formed which are very difiicult to removefrom the distillates. It is mybeliet that these latter sulphur compounds are principally carbon bisulphide, these carbon bisulphides being formed even when low'temperatures are used. It must be borne in mind that the carbon formedin cracking the charging oil, is formed bycracking said oilin the presence of the sulphur contained therein, and that the carbon thus liberated being in a nascent statejis in an ideal condition to comnearly as great as if there is any carbon Serial m. 49,455. aenewea October 5,1928.

bine with part of the sulphur to form carbon bisulphide. I p I c I have ascertained that whena certain oil is treated containing-a known amountof sulphur; ata low cracking temperature, that the dificulty ofremoving the sulphur from the distillates produced therefrom, is not when the same "oil with the sameamount of sulphur is subjected to higher cracking temperatures. My observation further indicates that as the cracking temperaturemaintained on the charging oil increases, the action of removing the sulphur from the distillate produced therefrom, increases until: a maximum temperature is reached, at which time all the sulphur is thus affected.

It is to be understood that my invention is applicable to allsubstances which contain sulphur, and which are subjected to crackifngltemperatures to produce a liquid motor One ofthe standard methods for treating the distillate products'of petroleum oil, is to subject these products separately to the action otsodium plumbite, sulphuric acid, caustic soda, with intervening water washes, the choice of succession of steps for introducing these refining agents being regulated at will .by the refiner. The product may then be subjected; to steam distillation. This standard method of treatment efi ectively removes all of the sulphureted hydrogenthat may be in solution insa-id distillate, and-possibly part of the carbon bisulphide and other deleterious compounds. however, that unless,as heretofore pointed out, an excessive amount of sulphuric acid is used which results in an excessive loss of distillate, that the 'finished product will still contain alarge percentage of sulphur and will be unstable, goingofi color on standing, particularly when exposed to the sunlight.

In my opinion this is due to the carbon ASSIGNOR'TOUNIVERSAL OILI'RODUOT I It has beenfound bisulphide compounds remaining in the distillate. It isa known'fact' that carbon bisulphide has a low vaporizing.temperature. Therefore, one would be led to believe that bi'sulphidein the oil,

some of the carbon bisulphides distill over with the overhead product, and possibly the remainder stays in the still held there by some chemical combination with. the residue,

which combination is not broken down'until higher temperatures amu ed. Part of the carbon bisulphide distilling over with the V overhead product of the-steam distillation is dissolved out of said overhead product with the steam as 'theroverhead product is condensed, said carbon bisulphide being carried outin'the-water; -In other'words,the-overhead, product is thoroughly scrubbed with thewater'of the steam and while the carbon hisnlphide is but very slightly soluble in watenyet, there is such a small trace of it in the overhead" product and such a great nuin ber of. pounds of steam used per poundof overhead vapors, thatit would be sufiicien't' to remove a bisulphide. To overcome many of the difficulties enumerated in the foregoing-explanation, and as a feature of the present invention, thefdistilgreat deal of this carbon late produced .from cracking may be subjected' to calciumhydrosulphide mixed with water,- the formula of whichis V saidcalcium hydrosulphide'inixed with water being converted into calcium hydroxyhydrosulphide which -further reacts with carbon bisulphide as follows: V acaoHsH +"os2 e s n Ca 011) oaos... It may be that this compound is not a pure compound of carbon bis'ulphide, but the com pound thatmay be causing all the trouble is oilile that readily breaks down to carbon bis'ulpida Myi'nvention contemplates variousmethods of subjecting said distillate to the above treatment, and includes as one of'theffeatures of the invention the process of passing the undesirablegases and distillate produced from cracking separately or together through a solution of calcium hydrate preferably, but

not necessarily,

' able, sugar may be added as these products are discharged from the cracking plant. If desirto the calcium hydrate solution in order to make the calcium hydrate more soluble in water,if itispreferred to'maintain this calcium hydrate solution a-tsa-n elevated temperature The sulphureted hydrogen contained in the uncon-- 'densable gas and in the distilla'te's produced rom the cracking reaction reacts with the calcium hydrate to form calcium hydrosulphide-Ca(OH) plus 2H S forming Ca(S I-l) plus H O thus forming the above described hydroxyhydrosulphid'e which lat.

, distillate and ter reacts with carbon bisulphide as follows i 2GaOH,SI-I CS SH Ca ,0aCSg.

a second tank containing thelcalcium hydrate to form anothersi'milar reaction; third-in then passing the gas and distillate, or the distillate alone from this second tank back to the first tank so thatthe hydroxyhydro sulphide may react With the carbon bisulphi-de and then pass with the distillate or the gas through a'thirdtank containing'calcium hydrate to remove the 'sulphu-reted hydrogen. The success of this reaction will bedepende'nt upon bringingthe gases and distillate into intimate contact with the calciumhydrate solution and hydroxyhydrosulphide so that-the sulphur content in the'distillate and gas may be acted upon'by these chemicals. Mechanical washers may be interposed between the separate tanks if found desirable, and other devices for'washing and mixing the chemicals with the distillate and gas'may be employed.

By the above method of treatment, it will be readily-seen'thatthe'sulphureted hydrogen which is a very objectionable compound is not only extracted from the gas and distillate, but is utilized'when removing the other objectionable compounds in the distillate and gas which are not removeddirectly by the calciu'mhydrate. V I v Y It will be readily seen therefore, that'in order to carry on the process, it is only necessary to-purch'ase calcium hydroxide, which is a relatively non-expensive chemical.

If found desirable", the di'stillatemay then be thoroughly washed and subjected to a weak solution of sulphuric acid and caustic. Ifthe distillate then has the required final boiling point, it is ready for the market. If this linal boi lin-g point 'isfltoohigh the distillate -can be "subjected to the usual steam distillation. ractically the same results can be obtained by using instead of calcium hydrate, ammonium sulphide the presence of polysulphides which combine and eventually form ammonium thiooarbonate. Wh'en using ammonium sulphide I may inject this aqueous solution into the vapors of the low boiling point distillate mingled with "the uncondensa blegases at a point where they enter the condensing coi l,--or at any other I point. Ammonium sulphide in the presence of su lphureted hydrogen'gas will react with the carbon bisulphide compounds in the oil and the condensed distillate-may then be washed and subjected to a light acid treatment. It will be found that the sulphurcontent of the takes place,

low boiling point distillate will have been ahnost entirely, if not completely, removed.

I claim as my invention:

1. A process for removing sulphurous compounds from hydrocarbon distillates in the presence of hydrogen sulphide, consisting in initially charging the distillate to a zone containing calcium hydrate and water wherein hydroxy hydrosulphide is formed as a reaction product, in thereafter diverting the supply of distillate to a second zone containing calcium hydrate and water, wherein a reaction similar to the reaction in the first zone in passing the distillate from said second zone back to the first zone wherein the carbon bisulphide contained in the distillate will react with the hydroxy hydrosulphide to eliminate the carbon bisulphide from the distillate, 'n thereafter subjecting the distillate in an independent zone to treatment with calcium hydrate and water to remove therefrom any sulphuretedhydrogen.

2. A step in the process of refining cracked products of hydrocarbon oil which consists in subjecting said products to the action of cale cium hydroxyhydrosulphide. V

3. A process for removing sulphur compounds from hydrocarbon distillates in the presence of hydrogen sulphide which consists in subjecting the calcium hydrate and Water whereby calcium hydroxyhydrosulphide is formed asa reaction product, which in turn will react to' eliminate carbon bisulphide from the dis-- tillate'.

CARBON P. DUBBS.

distillate to the action of i 

